Insecticidal haloido-alkylene esters of caprylphenoxyacetic acid



Patented Oct. 12, 1948 UNITED STATES PATENT OFFICE INSECTICIDALHALOIDO-ALKYLENE ESTERS OF CAPRYLPHENOXYACETIC ACID William F. Hester,Drexel Hill, and W E Craig, Philadelphia, Pa., assignors to Rohm & HaasCompany, Philadelphia, Pa., a corporation of Delaware N Drawing.Application June 14, 1945, Serial No. 599,508

18 Claims. (01. 167-30) This invention relates to new compounds and toinsecticidal compositions comprising as an active agent one of saidcompounds, esters of caprylphenoxyacetic acid, in which the alcoholportion contains an allrylene chain, which may be interrupted by oxygenand which carries a haloid, and a carrier therefor. These toxic agentsare of the formula One of the most eflective types of such groups isshown in the present application to be a haloidoalkylene group or ahaloido-alkylene group the hydrocarbon chain of which is interrupted byoxygen, in which groups the alkylene chains have two or three carbonatoms, being in particular ethylene or propylene groups. Thecaprylphenyl nucleus may contain such substituents as chlorine, bromide,nitro, amino, or alkyl (in addition to the capryl group), etc.Insecticidal compositions based upon the esters of the composition maybe safely and effectively applied to living plants for the control ofinsects thereon, particularly soft-bodied insects, with considerableadvantage,

The esters of this invention may be prepared from substituted orunsubstituted caprylphenoxyacetic acids by esterlfying reactions withhalohydrins, reactions with haloethyl ethers, or reactions withcyanohydrins. The usual chlorine or bromine of such groups may readilybe replaced with iodine or with such halogenoids as the thiocyanoorcyano-groups, which are classed as haloids or halogenoids and, in thisparticular type of compound, appear generally equivalent to the halogensproper. Procedures for varying the substituents will be obvious to thoseskilled in the art.

Esters of the above type are mixed with a carrier to form theinsecticidal compositions of this invention. The carrier may be aninnocuous solvent therefor or a finely divided solid. Such compositionsmay also contain dispersing, spreading, and/or sticking agents. Thecompositions may be applied in aqueous sprays or dust to living plantsinfested with insects.

Further details are given in the following illustrative examples.

Example 1 Preparation of B-chlomethyl caprylphenozyacetate.A mixture of529 grams of caprylphenoxyacetic acid and 101 grams of phosphorustrichloride was stirred for two hours at to C. The phosphorus acid whichresulted in the reaction separated as a viscous lower layer, from whichthe upper layer of caprylphenoxyacetyl chloride was decanted. To 544grams of the acid chloride there was slowly added 200 grams ofcommercial ethylene chlorohydrin, with stirring. As reaction occurred,the temperature of the resulting mixture rose to 51 C. and hydrogenchloride was evolved. The reaction mixture was then stirred for twohours, while it was maintained at 7075 C. It was then cooled and washed,first with water, then with a 2% sodium sulfate solution, and then threetimes with a 2% calcium chloride solution. It was then concentrated on awater bath under reduced pressure. A clear brown oil was obtained which,by analysis, was found to contain 91.5% oi. fi-chloroethylcaprylphenoxyacetate and 8.4% of caprylphenoxyacetic acid. While thisoil can be further purified-by removal of the acid, charcoaling,extraction, and similar methods, it was not found necessary to do so,since the crude product as first obtained proved to be a potent toxicagent for insects.

Instead of the caprylphenoxyacetic acid used above, there may besimilarly employed equivalent weights of substituted caprylphenoxyaceticacid, such as bromoor chloro-caprylphenoxyacetic acid ormethylcaprylphenoxyacetic acid. The esters obtained are all effectivetoxic agents in insecticidal compositions.

Instead of the ethylene chlorohydrin used above, there may be usedethylene bromohydrin or propylene chloroor bromohydrins.

Example 2 Preparation of B- (B'-chl0roeth0:ny) -ethylcaprylphenoxyacetate.-A mixture of 119 grams of caprylphenoxyaceticacid, 258 grams of fi, B-dichlorodiethyl ether, 10 grams of 35% aqueousdimethylamine, and 43.5 grams of a 50% aqueous sodium hydroxide solutionwas stirred and heated under reflux conditions with a trap in the returnpressure. The yield was 87 grams or dark brown acidulated water. The oillayer was separated and heated on an oil bath up to 250 C. at 30 mm;

This removed excess dichloroethyl ether and left 155 grams of an oilyresidue which contained, by

analysis, 86% of fi-(W-chloroethoxy) -ethy1 caprylphenoxyacetate.

Instead of the dichloroethyl, ether used above.

' there may be used fi,p'-dibrom'oethyl ether or the analogousdichlorotriglycol or dibromotriglycol to form chloroorbromo-ethoxyethoxyethyl caprylphenoxyacetates. Instead ofcaprylphenoxyacctic acid used above, there may be used a substitutedcaprylphenoxyacetic acid. I

The chloroor bromo-ethyl groups in the above compounds may be convertedto cyano or thiocyano-groups by reaction with metal cyanides and metalthiocyanates, respectively, or to the iodo compounds by reaction with aniodide, such as sodium or potassium iodide, as illustrated by thefollowing examples.

Example 3 A reaction mixture consisting of 408.5 grams (1.25 mols) of,B-chloroethyl caprylphenoxyacetate, 145 grams (1.75 mols) of 98% sodiumthiocyanate, 204 grams of methyl isobutyl ketone, and traces of copperpowder and sodium iodide was stirred for twenty-eight hours at areaction temperature of 129-139 C. After being cooled, the inorganicsalts were filtered off and washed with petroleum ether; and thecombined filtrates were washed three times with water, dried overcalcium chloride, and concentrated in a boiling water bath at reducedpressure to give 411 grams of viscous brown oil-which contained, byanalysis, 2.74% of nitrogen. The calculated nitrogen value forp-thiocyanoethyl caprylphenoxyacetate is 1 Example 4 A reaction. mixtureconsisting of 93 grams of 19- (p'-chloroethoxy) -ethylcaprylphenoxyacetate of 85% purity by chlorine analysis, 29 grams of 98%sodium thiocyanate, 50 grams of methyl isobutyl ketone, and a trace ofcopper powder was or Example 5 To 70 grams (0.2 mol) ofcapryldichlorophenoxyacetyl chloridethere was added at 26-36 C. over atwenty-minute period 29.4 grams (0.2 mol) of fl-thiocyano-p'hydroxyethylether. The resulting solution was stirred for two hours in a boilingwater bath. 'Since no appreciable hydrogen chloride was evolved, thesolution was cooled and 16 grams (0.2 mol) of pyridine was added at19-34 C. After the mixture was stirred for four hours at roomtemperature, ethylene dichloride was added. The resulting mixture waswashed with water three times, dried over calcium chloride, andconcentrated at 100 C. and 25 mm.

oil. This contained, by analysis, 2.87% of nitrogen and 15.17% ofchlorine. which are 95% and 99% of the n'itrogen and chlorine valuescalculated for 3- (p"-thiocyanoethoxy) -ethylcapryldichlorophenoxyacetate.

' Esters of the type described above are effective toxic agents ininsecticidal compositions, as has been -indicated.- They may be used asthe sole 'toxicant in a given composition or they may be used inconjunction with other toxic agents, such as naturally. occurringagents, including pyreth- 'rins, rotenone, and nicotine, or otherorganic thiocyanates than the thiocyano-alkylene orthiocyano-alkoxyalkylene esters-of this invention, and

a volatilizable solvent andthe solution applied to such solid withsubsequent removal of the solvent.

As a solid carrier, there may be used one or more of such materials asclay, talc, pyrophyllite, asbestine, magnesium carbonate, chalk,diatomaceous earth, alum sludge, lime, and the like. There may beincorporated with such solids spreaders orstickers.

Concentrations of the toxicants may advisedly be varied from one half toten per cent in such compositions. These may be applied as dusts, orthey may be taken up in water and applied in the forms of sprays.

Typical formulations involving solid compositions follow:

Parts Toxicant 1 Talc 98 Spreader or sticker 1 Parts Toxicant 2 Alumsludge 48 Lime 48 Soya bean oil 2 0n the other hand, the estersdescribed above may be taken up-with a liquid carrier. Innocuous organicsolvents are generally suitable for this purpose. Typical of these arepine oil-s, higher liquid alcohols such as octyl alcohol orcyclohexanol, ketones such as hexyl methyl ketone,

or various vegetable or mineral oils, or mixtures of such solvents.

Advantageously, such solvent compositions may be made with asolvent-soluble emulsifier or a dispersing agent which renders thecomposition self-dispersing in water. There may otherwise be used anemulsifying agent at the time of preparation of a spray from the liquidcomposition.

Typical liquid compositions may be made from one part of the esters ofthe above type, one to ten parts of an organic solvent, and one tenth toone part of an organic solvent-soluble dispersing agent, such as apolyalkoxyether alcohol prepared from a long-chained alcohol or phenoland an alkylene oxide, for example, diisobutylpolyethoxy ethanol, or acondensate of polyglycerol and a higher fatty acid with maleic acid, ora petroleum sulfonate. These compositions are self dispersing when addedto water.

Tests against various insects are'reported below.

Ei'ample 6 (a) fi-chloroethyl caprylphenoxyacetatc was taken up in clayand this mixture diluted with talc to give a dust containing 2% of theactive agent. This dust was applied to bean plants infested withleafhopper nymphs. The kill obtained, 78%, may be compared with that of32% resulting under the same conditions with a com- :mercial rotenonedust.

(b) Another preparation of the above ester was dissolved in pine oil andpetroleum sulfonate in a ratio of three to four to one for these threecomponents. When this composition was diluted with water to give adilution of one part of ester in 350 parts of water and sprayed on youngcabbage plants infested with aphids, a kill of 79% was obtained. Therewas no foliage injury.

(0) When the above spray was applied to bean plants infested with redspiders at a dilution of 1 to 264, a 98% kill was obtained, againwithout any evidence of foliage injury.

(d) A 1% dust made with magnesium carbonate, when applied to bean plantsinfested with Mexican bean beetle larvae, gave a control of (e) A 1%solution of the above ester was made in volatile hydrocarbons andapplied to woolen cloth, which was then dried and exposed to theatmosphere for two months. Samples of this cloth placed in a cage withclothes moths killed the moths.

Example 7 (a) A dust containing 2% B-thiocyanoethyl capiylphenoxyacetatewas applied to nasturtiums infested with aphids. A kill of 79% wasobtained. No foliage injury resulted.

(b) A solution was made of one part of fl-thiocyanoethylcaprylphenoxyacetate in two parts of pine oil and one part of petroleumsulfonate added. This composition was stirred into water at theproportion of one part to about two hundred parts and the resultingemulsion sprayed onto young cabbage plants infested with aphids. A killof 75% was obtained without foliage injury.

(0) When the above spray was applied to bean plants infested with redspiders at a dilution of l to 220, a 79% kill was obtained.

Example 8 (a) A mixture of capryl- C6H4OCH2COOC2H4OC2H4C1 was made withthe condensate of polyglycerol, coconut fatty acids, and maleic acid inthe ratio of five parts to four parts and eleven parts of pine oiladded. This composition was stirred into water and applied in the formof a spray at a concentration of one part of the ester to 1600 parts ofwater to nasturtium plants infested with plants infested with beanbeetle larvae, a control aphids. A kill of 75% was obtained. There wasno foliage injury.

(b) A similar composition applied to bean plants infested with redspiders, but diluted to give an aqueous spray containing one part of theester in 1200 parts of water, gave a kill of 97 (c) A solution of 1% ofthe above ester in volatile hydrocarbons was applied to woolen cloth,which was dried and exposed for several months before being tested. Thistreated cloth, when exposed to carpet beetles, permitted little feedingthereon and killed all of the carpet beetles.

(d) Another sample of the above ester was mixed with magnesium carbonateand the resultof 76% was obtained.

Example 9 (a) A composition was prepared from five parts ofcapryl-C5H40CH2COOC2H4OC2H4SCN, four parts of the condensate ofpolyglycerol, coconut acid, and maleic acid, and eleven parts ofcottonseed oil and pine oil mixture. When this composition was dispersedin water and applied to nasturtium plants infested with aphids, a killof 92% was obtained.

(b) Another sample of the above ester mixed with magnesium carbonate anddispersed in water at one pound of ester per one hundred gallons ofwater was applied as a spray to bean plants infested with bean beetlelarvae. A control of 86% was obtained.

(0) A standard Feet-Grady fly test of a 2% solution of the above esterin kerosene gave a knockdown of 89% and a kill of .-8 vs. 0. T. I. Thespray gave no irritation.

We claim:

1. Compounds of the formula Capryl-Ph-OCH2COOCnH2n (OCnHah) mX which nhas a value of two to three, inclusive.

2. Compounds of the formula Capry1-Ph-OCH2COOCnH2n(OCnI-hn) Cl whereinPh is a phenyl nucleus, m is a number from zero to two, inclusive, andCnHZn is an alkylene chain of at least two carbon atoms in which n has avalue of two to three, inclusive.

3. Compounds of the formula Capryl-Ph-OCHzCOOCfl-IzMOCd-Im) mSCN whereinPh is a phenyl nucleus, m is a number from zero to two, inclusive, andCHI-Ian is an alkylene chain of at least two carbon atoms in which n hasa value of two to three, inclusive.

4. Compounds of the formula Capryl-Ph-OCHzCOOCI-IzCI-h (OCHzCHz) mXwherein Ph is a phenyl nucleus, m is a number from zero to two,inclusive, and X is a haloid from the group consisting of chlorine,bromine, iodine, thiocyanoand cyano-groups.

5. Compounds of the formula Capryl-Ph-OCH2COOCH2CH2(OCH2CH2mCl whereinPh is a phenyl nucleus and m is a number from zero to two, inclusive.

6. Compounds of the formula Capryl-Ph-OCHzCOOCHzCHz(OCHzCl-h)mSCNwherein Ph is a phenyl nucleus and m is a number from zero to two,inclusive.

'7. A compound of the formula suitable for use on plants which comprisesa carrier and a compound of the formula CaptYl-Ph-OCHzCOOi'hHm OCsHis)1.x

wherein Ph is a phenyl nucleus, m is a number from zero to two,inclusive, and Catnip is an alkylene chain of at least two carbon atomsin which n has a value of two to three. inclusive.

12. An insecticidal composition particularly suitable for use on plantswhich comprises a carrier and a compound of the formulaCapryI-Ph-OCHaCOOCnHsMOCnHznMSCN wherein Ph is a phenyl nucleus, m is anumber from zero to two, inclusive, and C1|H2n is an alkylene chain ofat least two carbon atoms in which n has a value of two to three,inclusive.

13. An insecticidal composition particularly suitable for use on plantswhich comprises a carrier and a compound of the formula Capryl-Ph-OCH:COOCH2CH: (OCHoCHz) mX wherein Ph is a phenyl nucleus, m is anumber from zero to two, inclusive, and X is a haloid from the groupconsisting of chlorine, bromine, iodine, thiocyanoand cyano-groups.

14. An insecticidal composition particularly suitable for use on plantswhich comprises a carrier'and a compound of the formulaCapryl-Ph-CI-h0O0CI-IaCHs(OCHi-CH:)1||Cl wherein Ph is a phenyl nucleusand m is a number from zero to two, inclusive.

15. An insecticidal composition particularly suitable for use on plantswhich comprises a carrier and a compound of the formulacaprylh-ocmcoocmcmmcmcnhmscn wherein Ph is a phenyl nucleus and m is anumber from zero to two, inclusive.

16. An insecticidal composition particularly suitable for use on plantswhich comprises a carrier and a compound of the formula 17. Aninsecticidal composition particularly suitable for use on plants whichcomprises a carrier and a compound of the formulacepryl-cemwcrncoocimocimscn 18. An insecticidal composition particularlysuitable for use on plants which comprises a carrier and a compound ofthe formula CapryI-CeHh-OCHzCOOCzI-LSCN W E CRAIG.

REFERENCES orrEn v The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,021,095 Grether Mar. 26, 19122,179,209 Daimler et a1. NOV. 7, 1939 2,239,079 Coleman et a1. Apr. 22,1941 Weirich .i Oct. 20, 1942

